US5023346A - Process for the production of cyclic carbonic acid esters - Google Patents

Process for the production of cyclic carbonic acid esters Download PDF

Info

Publication number
US5023346A
US5023346A US07/434,443 US43444389A US5023346A US 5023346 A US5023346 A US 5023346A US 43444389 A US43444389 A US 43444389A US 5023346 A US5023346 A US 5023346A
Authority
US
United States
Prior art keywords
compound
reaction
diol
residue
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07/434,443
Inventor
Norbert Schon
Hans-Josef Buysch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Assigned to BAYER AKTIENGESELLSCHAFT reassignment BAYER AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BUYSCH, HANS-JOSEF, SCHON, NORBERT
Application granted granted Critical
Publication of US5023346A publication Critical patent/US5023346A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C07D321/02—Seven-membered rings
    • C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings

Definitions

  • This invention relates to a process for the production of cyclic carbonic acid esters using catalytic quantities of an N-heterocyclic aromatic compound.
  • aliphatic cyclic carbonates can be produced from the basic diols and phosgene with addition of equivalent quantities of a base, preferably an amine base (Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Vol. E 4 (1983), pages 83 et seq.).
  • a base preferably an amine base
  • 1,2-diols can be converted into the corresponding 5-ring carbonates in high yields in this way, lower yields of the corresponding cyclic carbonates are obtained with 1,3-diols and relatively long-chain ⁇ , ⁇ -diols (J. Org. Chem. 24 (1959), 1873).
  • carbonic acid esters may also be used for the production of cyclic carbonic acid esters by transesterification (Houben-Weyl, Vol. E 4 (1983), pages 88 et sec.).
  • this process involves an additional step because the carbonic acid esters required for the transesterification have to be prepared beforehand, for example from phosgene.
  • the object of the present invention is to provide a process by which cyclic carbonic acid esters can be obtained in high yields from phosgene and diols without large (substantially equivalent) quantities of bases having to be used and without any need for complicated working-up.
  • the present invention relates to a process for the production of cyclic carbonic acid esters corresponding to the following formula ##STR1## by reaction of compounds corresponding to the following formula
  • A is a binding link typically encountered in carbonic acid chemistry which is preferably capable of forming monomeric cyclic carbonates, more especially the residue of an aliphatic diol containing 3 to 18 carbon atoms, the residue of a carbocyclic or heterocyclic, non-aromatic diol containing 3 to 8 ring members, the residue of an ether-group-containing aliphatic diol containing up to 5 ether groups and up to 18 carbon atoms or the residue of an aromatic or araliphatic dihydroxy compound containing one or two aromatic nuclei, both OH groups in formula (II) being primary or phenolic OH groups and
  • z in formula (I) is an integer of from 1 to 4.
  • reaction is carried out in the presence of catalytic quantities of a nitrogen-containing compound K in which at least one nitrogen atom is a member of an aromatic ring.
  • the catalyst K is preferably used in a quantity of from 0.01 to 5% by weight, based on compound II.
  • Preferred compounds corresponding to formula (II) are, in particular, the following compounds
  • the index m is an integer of from 1 to 16.
  • R 1 and R 2 independently of one another represent hydrogen, alkyl, more especially C 1 -C 6 alkyl; alkenyl, more especially allyl; aryl, more especially phenyl; aralkyl, more especially benzyl, the radicals mentioned optionally being substituted, or halogen, more especially fluorine, chlorine, bromine or iodine, nitro or OH.
  • R 1 and R 2 are C 1 -C 6 alkyl, allyl, phenyl, benzyl, halogen, such as fluorine, chlorine, bromine or iodine, nitro, di(C 1 -C 4 -alkyl)-amino, hydroxy, hydroxymethyl, C 1 -C 4 alkoxymethyl, allyloxymethyl, halomethyl, a radical corresponding to the following formula ##STR3## or, together, methylene.
  • the aromatic nuclei mentioned may in turn be substituted by the halogen mentioned, nitro, methyl, ethyl, methoxy or ethoxy.
  • Q is a cyclic system containing 3 to 8 and preferably 3 to 6 ring members and may be, for example, a 1,1-bonded cyclopropane, cyclobutane, cyclopentane or cyclohexane ring, a 3,3-bonded oxetane, thietane, thietane-1-oxide, thietane-1,1-dioxide ring or a 1,2-bonded cyclobutane ring.
  • the index o is an integer of from 1 to 5 and preferably from 1 to 3.
  • the indices p and q independently of one another stand for the numbers 0, 1 or 2, the sum of p+q being ⁇ 1.
  • the substituents R 3 and R 4 independently of one another are hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen, such as fluorine, chlorine or bromine, or nitro. R 3 and R 4 together may even represent a condensed, further aromatic nucleus. In addition, R 3 or R 4 may also be phenyl.
  • X may be a single bond, a binding link, more especially an optionally substituted alkyl radical, particularly methylene and ethylene, a hydrocarbon chain containing 1 to 4 carbon atoms, oxygen, sulfur, --SO-- or --SO 2 --.
  • R 3 and R 4 are as defined above.
  • Examples of compounds corresponding to formula (III) are propane-1,3-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, decane-1,10-diol, dodecane-1,12-diol, octadecane-1,18-diol, 2,2-substituted propane-1,3-diols, such as 2-methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-ethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2-t-butyl-2-methylpropane-1,3-diol,2-butyl-2-methylpropane-1,3-diol,2-
  • Examples of compounds corresponding to formula (IV) are cyclopropane-1,1-dimethanol, cyclobutane-1,1-dimethanol, cyclopentane-1,1-dimethanol, 1-cyclohexene-4,4-dimethanol, cyclohexane-1,1-dimethanol, cyclobutane-1,2-dimethanol, 3,3-bishydroxymethyl oxetane and 3,3-bishydroxymethyl thietane.
  • Examples of compounds corresponding to formulae (V) and (VI) are diethylene glycol, triethylene glycol, o-hydroxymethylphenol and 1,2-bishydroxymethylbenzene.
  • Suitable bisphenols corresponding to formula (VII) are, for example, optionally substituted 2,2'-dihydroxybiphenyls, optionally substituted bis-(2-hydroxyphenyl)-methanes, such as bis-(2-hydroxy-5-methylphenyl)-methane, bis-(3-tert.-butyl-2-hydroxy-5-methylphenyl)-methane, bis-(5-chloro-2-hydroxyphenyl)-methane, bis-(3,5-dichloro-2-hydroxyphenyl)-methane,bis-(3,5-dimethyl-2-hydroxyphenyl)methane, optionally substituted 2,2-bis-(2-hydroxyphenyl)propanes, such as for example 2,2-bis-(3,5-dimethyl-2-hydroxyphenyl)-propane, and optionally substituted bis-(2-hydroxyphenyl)-oxides and sulfides.
  • 2,2'-dihydroxybiphenyls optionally substituted bis
  • B is the residue of a propane-1,3-diol, the residue of a polyethylene glycol or the residue of a bisphenol.
  • Propane-1,3-diols in this context are those corresponding to the following formula ##STR4## in which
  • R 11 and R 12 independently of one another represent hydrogen, C 1 -C 4 alkyl, phenyl, hydroxymethyl, C 1 -C 4 alkoxymethyl or allyloxymethyl or, together, may represent --CH 2 --O--CH 2 -- or, again together, may represent C 4 or C 5 alkylidene.
  • index r is the number 1 or 2.
  • the bisphenols also encompassed by formula (VIII) are those corresponding to formula (XI) ##STR5## in which Y is a single bond, methylene, oxygen or sulfur and
  • R 14 and R 15 independently of one another represent hydrogen, C 1 -C 4 alkyl or chlorine.
  • representatives of the dihydroxy compounds corresponding to formulae (IX), (X) and (XI) are, for example, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol,2-ethyl-2-methylpropane-1,3-diol,2,2-diethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2-methyl-2-butylpropane-1,3-diol,2-methyl-2-phenylpropane-1,3-diol,2,2-diphenylpropane-1,3-diol, trimethylolalkanes, such as trimethylolpropane and trimethylolethane, trimethylolpropane monopropyl ether, trimethylolpropane monoallyl ether, cyclopentane-1,1-dimethanol, cyclohexane-1,1-
  • the process according to the invention is carried out in the presence of from 0.01 to 5% by weight and preferably in the presence of from 0.1 to 2% by weight, based on the dihydroxy compound, of a compound K.
  • the compounds K are above all, nitrogen bases which carry the nitrogen atom in a aromatic 5- or 6-membered ring and, in addition, bear no functional groups which enter into firm bonds with phosgene, chlorocarbonic acid esters or carbonates under the reaction conditions, such as for example amino, hydroxy or mercapto groups.
  • other heteroatoms may be present in the ring system, including for example oxygen, sulfur or further N atoms.
  • the heterocycle may be condensed with other aromatic heterocycles or even with aromatic carbocycles.
  • Examples of the compounds K are pyridine, quinoline, isoquinoline; picolines, pyrazine, pyridazine and benzocondensed derivatives thereof; triazines, such as 2,4,6-trimethyl triazine, pyrazole, imidazole, triazole and thiazole and also the compounds substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 carbalkoxy or halogens such as 2-methyl imidazole, and also benzocondensed derivatives thereof, such as benzimidazole, benztriazole or benzthiazole.
  • the condensed benzene nuclei in systems such as these may in turn be substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 carbalkoxy, halogen or nitro.
  • Preferred compounds K for the process according to the invention are quinolines, picolines, benzimidazoles, pyrazoles, triazoles and benztriazoles, pyridines and imidazoles and especially picolines, pyridine and imidazole.
  • these compounds may of course also be used in the form of a mixture.
  • salts thereof for example hydrochlorides, hydrobromides, sulfates, etc. It is also possible to use salts from which the hydrochlorides may readily form in the reaction mixture, for example the formates, acetates, phosphates, carbamates, picrates and others.
  • the reaction of the dihydroxy compound with phosgene may be carried out in the melt of the dihydroxy compound or in solution, for which purpose inert solvents, such as hydrocarbons, halogenated hydrocarbons, esters, nitriles, ethers, amides, etc., may be used.
  • solvents such as hydrocarbons, halogenated hydrocarbons, esters, nitriles, ethers, amides, etc.
  • solvents are dichloromethane, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, diphenyl ether, chloronaphthalene, butyl acetate, benzonitrile, dimethyl acetaxide, N-methyl pyrrolidone.
  • the quantity of solvent used is not critical to the process according to the invention and may therefore vary within wide limits. For example, it is possible to use from 20 to 2,000% by weight and preferably from 100 to 1,000% by weight of solvent, based on the weight of the dihydroxy compound used.
  • Phosgene is generally used in a quantity 0.8 to 2 mol, preferably in a quantity of from 0.9 to 1.5 mol and more preferably in a quantity of from 0.9 to 1.1 mol per mol of the compound corresponding to formula (II) for the reaction according to the invention; the components may even be subsequently added.
  • the phosgene may be initially introduced in the solvent used, if any, or may even be added in the form of a solution to the (dissolved or suspended) dihydroxy compound initially introduced. Finally, the phosgene may be condensed into the solution, suspension or melt of the dihydroxy compound in liquid or gaseous form without any more solvent.
  • the N-heterocyclic aromatic compound to be used in accordance with the invention may be initially introduced together with the starting material or may even be added after the phosgene.
  • the reaction according to the invention is carried out at a temperature in the range from -20° C. to +300° C. and preferably at a temperature in the range from 120° to 250° C. in the case of aromatic compounds and at a temperature of from -20° to 140° C. in the case of aliphatic compounds.
  • the reaction may be carried out by increasing the temperature within the limits indicated in the course of the reaction. Where a solvent is used, it may be distilled off during the increase in temperature.
  • the reaction according to the invention is over when there is no further evolution of hydrogen chloride, even in the event of an increase in temperature.
  • inert gas for example nitrogen
  • the cyclic carbonic acid esters may be isolated from the reaction mixture by standard methods, for example by crystallization or distillation; in the case of high-boiling reaction products, vacuum distillation or high vacuum distillation may also be considered.
  • cyclic carbonic acid esters obtainable in accordance with the invention are valuable starting materials for homo- and copolycarbonates, duromer systems (EP-A 188 204) and copolymers of cyclic carbonic acid esters and lactams (DE-A 30 40 612).
  • Residues of hydrogen chloride were then removed by application of a low vacuum. Removal of the toluene and fractionation of the residue in vacuo left 121 g (93%) of a solid product (boiling point 142° to 146° C./10 mbar). Recrystallization from ethyl acetate gave 117 g (90%) of product (Mp. 108° to 109° C.). Further working up is unnecessary.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

Cyclic carbonic acid esters are produced by reaction of hydroxy compounds with phosgene in the presence of a heterocyclic compound containing at least one nitrogen atom as ring member in an aromatic ring.

Description

This invention relates to a process for the production of cyclic carbonic acid esters using catalytic quantities of an N-heterocyclic aromatic compound.
It is known that aliphatic cyclic carbonates can be produced from the basic diols and phosgene with addition of equivalent quantities of a base, preferably an amine base (Houben-Weyl, Methoden der organischen Chemie, 4th Edition, Vol. E 4 (1983), pages 83 et seq.). Whereas 1,2-diols can be converted into the corresponding 5-ring carbonates in high yields in this way, lower yields of the corresponding cyclic carbonates are obtained with 1,3-diols and relatively long-chain α,ω-diols (J. Org. Chem. 24 (1959), 1873). The working-up step of this process is complicated because the amine salts formed generally have to be removed by aqueous extraction (cf. J. Am. Chem. Soc. 73 (1951), 5779; U.S. Pat. No. 3,532,715), which leads to losses of yield, particularly in the case of water-soluble and readily hydrolyzable carbonates. In the same way as aliphatic diols, o,o'-bisphenols can also be reacted with phosgene and equivalent quantities of a nitrogen base to form cyclic carbonic acid esters (U.S. Pat. No. 3,221,025).
Instead of phosgene, carbonic acid esters may also be used for the production of cyclic carbonic acid esters by transesterification (Houben-Weyl, Vol. E 4 (1983), pages 88 et sec.). However, this process involves an additional step because the carbonic acid esters required for the transesterification have to be prepared beforehand, for example from phosgene.
Accordingly, the object of the present invention is to provide a process by which cyclic carbonic acid esters can be obtained in high yields from phosgene and diols without large (substantially equivalent) quantities of bases having to be used and without any need for complicated working-up.
The present invention relates to a process for the production of cyclic carbonic acid esters corresponding to the following formula ##STR1## by reaction of compounds corresponding to the following formula
HO--A--OH                                                  (II)
in which
A is a binding link typically encountered in carbonic acid chemistry which is preferably capable of forming monomeric cyclic carbonates, more especially the residue of an aliphatic diol containing 3 to 18 carbon atoms, the residue of a carbocyclic or heterocyclic, non-aromatic diol containing 3 to 8 ring members, the residue of an ether-group-containing aliphatic diol containing up to 5 ether groups and up to 18 carbon atoms or the residue of an aromatic or araliphatic dihydroxy compound containing one or two aromatic nuclei, both OH groups in formula (II) being primary or phenolic OH groups and
z in formula (I) is an integer of from 1 to 4
with phosgene, characterized in that the reaction is carried out in the presence of catalytic quantities of a nitrogen-containing compound K in which at least one nitrogen atom is a member of an aromatic ring.
The catalyst K is preferably used in a quantity of from 0.01 to 5% by weight, based on compound II.
Preferred compounds corresponding to formula (II) are, in particular, the following compounds
HO--CH.sub.2 --(--CR.sup.1 R.sup.2 --).sub.m --CH.sub.2 --OH (III),
saturated carbocyclic or heterocyclic compounds corresponding to the following formula
HO--CH.sub.2 --Q--CH.sub.2 --OH                            (IV),
aliphatic compounds containing ether groups corresponding to the following formula
HO--[(CH.sub.2 --).sub.2 --O--].sub.o --(CH.sub.2).sub.2 --OH (V)
and aromatic or araliphatic compounds corresponding to the following formulae ##STR2##
In formula (III), the index m is an integer of from 1 to 16.
R1 and R2 independently of one another represent hydrogen, alkyl, more especially C1 -C6 alkyl; alkenyl, more especially allyl; aryl, more especially phenyl; aralkyl, more especially benzyl, the radicals mentioned optionally being substituted, or halogen, more especially fluorine, chlorine, bromine or iodine, nitro or OH. Particularly preferred substituents R1 and R2 are C1 -C6 alkyl, allyl, phenyl, benzyl, halogen, such as fluorine, chlorine, bromine or iodine, nitro, di(C1 -C4 -alkyl)-amino, hydroxy, hydroxymethyl, C1 -C4 alkoxymethyl, allyloxymethyl, halomethyl, a radical corresponding to the following formula ##STR3## or, together, methylene. The aromatic nuclei mentioned may in turn be substituted by the halogen mentioned, nitro, methyl, ethyl, methoxy or ethoxy.
In formula (IV), Q is a cyclic system containing 3 to 8 and preferably 3 to 6 ring members and may be, for example, a 1,1-bonded cyclopropane, cyclobutane, cyclopentane or cyclohexane ring, a 3,3-bonded oxetane, thietane, thietane-1-oxide, thietane-1,1-dioxide ring or a 1,2-bonded cyclobutane ring.
In formula (V), the index o is an integer of from 1 to 5 and preferably from 1 to 3.
In formula (VI), the indices p and q independently of one another stand for the numbers 0, 1 or 2, the sum of p+q being ≧1. The substituents R3 and R4 independently of one another are hydrogen, C1 -C6 alkyl, C1 -C6 alkoxy, halogen, such as fluorine, chlorine or bromine, or nitro. R3 and R4 together may even represent a condensed, further aromatic nucleus. In addition, R3 or R4 may also be phenyl.
In formula (VII) X may be a single bond, a binding link, more especially an optionally substituted alkyl radical, particularly methylene and ethylene, a hydrocarbon chain containing 1 to 4 carbon atoms, oxygen, sulfur, --SO-- or --SO2 --. The substituents R3 and R4 are as defined above.
Examples of compounds corresponding to formula (III) are propane-1,3-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, decane-1,10-diol, dodecane-1,12-diol, octadecane-1,18-diol, 2,2-substituted propane-1,3-diols, such as 2-methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-ethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2-t-butyl-2-methylpropane-1,3-diol,2-butyl-2-methylpropane-1,3-diol, 2-allyl-2-methylpropane-1,3-diol, 2,2-diphenylpropane-1,3-diol, 2-methyl-2-phenylpropane-1,3-diol, 2,2-dibenzylpropane-1,3-diol, 2-chloro-2-nitropropane-1,3-diol, glycerol, 2,2,-bis-hydroxymethylpropane-1,3-diol, 2-alloyoxymethyl-2-ethylpropane-1,3-diol (TMP monoallyl ether), 2,2-bis-ethoxymethylpropane-1,3-diol (pentaerythritol diethyl ether), 2,2-bischloromethylpropane-1,3-diol and 2-methylenepropane-1,3-diol.
Examples of compounds corresponding to formula (IV) are cyclopropane-1,1-dimethanol, cyclobutane-1,1-dimethanol, cyclopentane-1,1-dimethanol, 1-cyclohexene-4,4-dimethanol, cyclohexane-1,1-dimethanol, cyclobutane-1,2-dimethanol, 3,3-bishydroxymethyl oxetane and 3,3-bishydroxymethyl thietane.
Examples of compounds corresponding to formulae (V) and (VI) are diethylene glycol, triethylene glycol, o-hydroxymethylphenol and 1,2-bishydroxymethylbenzene.
Suitable bisphenols corresponding to formula (VII) are, for example, optionally substituted 2,2'-dihydroxybiphenyls, optionally substituted bis-(2-hydroxyphenyl)-methanes, such as bis-(2-hydroxy-5-methylphenyl)-methane, bis-(3-tert.-butyl-2-hydroxy-5-methylphenyl)-methane, bis-(5-chloro-2-hydroxyphenyl)-methane, bis-(3,5-dichloro-2-hydroxyphenyl)-methane,bis-(3,5-dimethyl-2-hydroxyphenyl)methane, optionally substituted 2,2-bis-(2-hydroxyphenyl)propanes, such as for example 2,2-bis-(3,5-dimethyl-2-hydroxyphenyl)-propane, and optionally substituted bis-(2-hydroxyphenyl)-oxides and sulfides.
Particularly suitable compounds II for the process according to the invention are those corresponding to the following formula
HO--B--OH                                                  (VIII)
in which
B is the residue of a propane-1,3-diol, the residue of a polyethylene glycol or the residue of a bisphenol.
Propane-1,3-diols in this context are those corresponding to the following formula ##STR4## in which
R11 and R12 independently of one another represent hydrogen, C1 -C4 alkyl, phenyl, hydroxymethyl, C1 -C4 alkoxymethyl or allyloxymethyl or, together, may represent --CH2 --O--CH2 -- or, again together, may represent C4 or C5 alkylidene.
Polyethylene glycols which also fall within the scope of formula (VIII) are those corresponding to the following formula
HO--(CH.sub.2 --CH.sub.2 --O).sub.r --CH.sub.2 --CH.sub.2 --OH (X)
in which the index r is the number 1 or 2.
The bisphenols also encompassed by formula (VIII) are those corresponding to formula (XI) ##STR5## in which Y is a single bond, methylene, oxygen or sulfur and
R14 and R15 independently of one another represent hydrogen, C1 -C4 alkyl or chlorine.
Typical, but by no means exclusive, representatives of the dihydroxy compounds corresponding to formulae (IX), (X) and (XI) are, for example, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol,2-ethyl-2-methylpropane-1,3-diol,2,2-diethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2-methyl-2-butylpropane-1,3-diol,2-methyl-2-phenylpropane-1,3-diol,2,2-diphenylpropane-1,3-diol, trimethylolalkanes, such as trimethylolpropane and trimethylolethane, trimethylolpropane monopropyl ether, trimethylolpropane monoallyl ether, cyclopentane-1,1-dimethanol, cyclohexane-1,1-dimethanol and 3,3-bis-(hydroxymethyl)-oxetane; diethylene glycol and triethylene glycol; 2,2-dihydroxybiphenyl, bis-(5-methyl-2-hydroxyphenyl)-methane, bis-(3,5-dimethyl-2-hydroxyphenyl)-methane, bis-(5-chloro-2-hydroxyphenyl)methane and bis-(2-hydroxyphenyl)-oxide.
The process according to the invention is carried out in the presence of from 0.01 to 5% by weight and preferably in the presence of from 0.1 to 2% by weight, based on the dihydroxy compound, of a compound K. The compounds K are above all, nitrogen bases which carry the nitrogen atom in a aromatic 5- or 6-membered ring and, in addition, bear no functional groups which enter into firm bonds with phosgene, chlorocarbonic acid esters or carbonates under the reaction conditions, such as for example amino, hydroxy or mercapto groups. In addition to the nitrogen atom, other heteroatoms may be present in the ring system, including for example oxygen, sulfur or further N atoms. In addition, the heterocycle may be condensed with other aromatic heterocycles or even with aromatic carbocycles.
Examples of the compounds K are pyridine, quinoline, isoquinoline; picolines, pyrazine, pyridazine and benzocondensed derivatives thereof; triazines, such as 2,4,6-trimethyl triazine, pyrazole, imidazole, triazole and thiazole and also the compounds substituted by C1 -C4 alkyl, C1 -C4 alkoxy, C1 -C4 carbalkoxy or halogens such as 2-methyl imidazole, and also benzocondensed derivatives thereof, such as benzimidazole, benztriazole or benzthiazole. The condensed benzene nuclei in systems such as these may in turn be substituted by C1 -C4 alkyl, C1 -C4 alkoxy, C1 -C4 carbalkoxy, halogen or nitro.
Preferred compounds K for the process according to the invention are quinolines, picolines, benzimidazoles, pyrazoles, triazoles and benztriazoles, pyridines and imidazoles and especially picolines, pyridine and imidazole. Several of these compounds may of course also be used in the form of a mixture. In addition, instead of the free bases of these compounds, it is possible to use salts thereof, for example hydrochlorides, hydrobromides, sulfates, etc. It is also possible to use salts from which the hydrochlorides may readily form in the reaction mixture, for example the formates, acetates, phosphates, carbamates, picrates and others.
The reaction of the dihydroxy compound with phosgene may be carried out in the melt of the dihydroxy compound or in solution, for which purpose inert solvents, such as hydrocarbons, halogenated hydrocarbons, esters, nitriles, ethers, amides, etc., may be used. Examples of such solvents are dichloromethane, chloroform, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, diphenyl ether, chloronaphthalene, butyl acetate, benzonitrile, dimethyl acetaxide, N-methyl pyrrolidone.
The quantity of solvent used, if any, is not critical to the process according to the invention and may therefore vary within wide limits. For example, it is possible to use from 20 to 2,000% by weight and preferably from 100 to 1,000% by weight of solvent, based on the weight of the dihydroxy compound used.
Phosgene is generally used in a quantity 0.8 to 2 mol, preferably in a quantity of from 0.9 to 1.5 mol and more preferably in a quantity of from 0.9 to 1.1 mol per mol of the compound corresponding to formula (II) for the reaction according to the invention; the components may even be subsequently added. The phosgene may be initially introduced in the solvent used, if any, or may even be added in the form of a solution to the (dissolved or suspended) dihydroxy compound initially introduced. Finally, the phosgene may be condensed into the solution, suspension or melt of the dihydroxy compound in liquid or gaseous form without any more solvent. The N-heterocyclic aromatic compound to be used in accordance with the invention may be initially introduced together with the starting material or may even be added after the phosgene.
The reaction according to the invention is carried out at a temperature in the range from -20° C. to +300° C. and preferably at a temperature in the range from 120° to 250° C. in the case of aromatic compounds and at a temperature of from -20° to 140° C. in the case of aliphatic compounds. The reaction may be carried out by increasing the temperature within the limits indicated in the course of the reaction. Where a solvent is used, it may be distilled off during the increase in temperature. During the reaction according to the invention, it is possible to change from a relatively low-boiling solvent to a relatively high-boiling solvent This can be done very easily by distilling off the low-boiling solvent during the increase in temperature and, at the same time, introducing the higher-boiling solvent into the reaction mixture either continuously or in batches. The reaction is then completed in the higher boiling solvent or, where all the solvents used are completely distilled off, even in a melt of the cyclic carbonic acid ester produced. In the reaction of aliphatic dihydroxy compounds or aliphatic dihydroxy compounds containing ether groups or cyclic dihydroxy compounds containing non-aromatic groups, it has proved to be of advantage to apply a temperature in the range from -20° C. to +140° C. and preferably in the range from -5° C. to +120° C. It is of particular advantage in this regard to begin the reaction at a temperature in the range from -5° C. to +50° C. and preferably in a temperature in the range from -5° C. to +15° C. In this variant also, the temperature may be increased during the reaction in the described manner.
The reaction according to the invention is over when there is no further evolution of hydrogen chloride, even in the event of an increase in temperature. To remove residues of hydrogen chloride, it may be advisable either to apply a vacuum or to pass a stream of inert gas (for example nitrogen) through the reaction mixture.
The cyclic carbonic acid esters may be isolated from the reaction mixture by standard methods, for example by crystallization or distillation; in the case of high-boiling reaction products, vacuum distillation or high vacuum distillation may also be considered.
The yields of cyclic carbonic acid esters are generally very high. In the case of 6-membered, aliphatic compounds they are generally higher than 90% of the theoretical yield. The crude products are generally pure enough for many applications.
The cyclic carbonic acid esters obtainable in accordance with the invention are valuable starting materials for homo- and copolycarbonates, duromer systems (EP-A 188 204) and copolymers of cyclic carbonic acid esters and lactams (DE-A 30 40 612).
EXAMPLE 1 5,5-dimethyl-1,3-dioxan-2-one
198 g (2.00 mol) phosgene were introduced over a period of 1,5 h at 0° to 5° C. into a suspension of 208 g (2.00 mol) 2,2-dimethylpropane-1,3-diol and 600 ml dry dichloromethane, followed by stirring at that temperature until the initially vigorous evolution of hydrogen chloride had abated. The discharge of phosgene was prevented by an effective reflux condenser (dry ice). The solvent was then removed in vacuo, 500 mg (0.2% by weight) imidazole and 500 ml toluene were added and the reaction was completed by slowly increasing the temperature to 110° C. until the evolution of hydrogen chloride had stopped (3 hours). Residues of hydrogen chloride were then removed by application of a low vacuum. Removal of the toluene and fractionation of the residue in vacuo left 121 g (93%) of a solid product (boiling point 142° to 146° C./10 mbar). Recrystallization from ethyl acetate gave 117 g (90%) of product (Mp. 108° to 109° C.). Further working up is unnecessary.
EXAMPLE 2 Cyclic carbonate of 2,2'-dihydroxybiphenyl
150 g (1.50 mol) phosgene were introduced over a period of 2.5 h at 115° to 120° C. into a solution of 186 g (1.00 mol) 2,2'-dihydroxybiphenyl and 1.00 g imidazole. To complete the evolution of hydrogen chloride, the solution was heated for 2 hours until a reflux began, after which the solvent was distilled off in vacuo. The solid residue (212 g) was distilled in a high vacuum. A colorless, crystallizing distillate (Bp. 126° to 130° C./0.35 to 0.5 mbar) was obtained in a yield of 189 g (89%). Mp.: 99° to 100° C. (from diisopropyl ether); IR: 1805 cm-1 (C═O).
Further working up is unnecessary.

Claims (9)

We claim:
1. A process for the production of cyclic carbonic acid esters corresponding to formula I ##STR6## by reaction of compounds corresponding to formula II
HO--A--OH
in which
z is an integer of from 1 to 5 and
A is a binding link selected from the residue of an aliphatic diol containing 3 to 18 carbon atoms, the residue of a non-aromatic, carbocyclic or heterocyclic diol containing 3 to 8 ring members, the residue of an ether-group-containing aliphatic diol containing up to 5 ether groups and up to 18 carbon atoms, and the residue of an aromatic or araliphatic dihydroxy compound containing one or two aromatic nuclei
with phosgene, wherein the reaction is carried out in the presence of 0.01 to 5% by weight, based on the weight of the compound of formula II, of a catalytic compound which contains at least one nitrogen atom as a member of an aromatic ring system.
2. A process as claimed in claim 1, wherein compound II has the following structure
HO--B--OH
in which
B is the residue of a propane-1,3-diol, the residue of a polyethylene glycol or the residue of a bisphenol which remains after the removal of two OH groups.
3. A process as claimed in claim 1, wherein the catalytic compound is used in a quantity of from 0.1 to 2% by weight, based on compound II.
4. A process as claimed in claim 1 wherein the catalytic compound is selected from a pyridine, quinoline, picoline, imidazole, benzimidazole, pyrazole, triazole or benzotriazole.
5. A process as claimed in claim 1, wherein the reaction is carried out in the presence of an inert solvent.
6. A process as claimed in claim 1, wherein from 0.8 to 2 mol phosgene are used per mol of compound corresponding to formula (II).
7. A process as claimed in claim 1, wherein the temperature is increased during the reaction and, where a solvent is used, the solvent is distilled off, the solvent distilled off being replaced by a solvent of higher boiling point during the increase in temperature and the reaction being completed in the solvent of higher boiling point or, where all solvents are completely distilled off, in the melt of the reaction product.
8. A process as claimed in claim 1, wherein compound II is an aromatic compound and the reaction is carried out at a temperature in the range from 120° to 250° C.
9. In a process for preparing a cyclic carbonic acid ester by reacting a diol with phosgene, the improvement comprising carrying out the reaction in the presence of 0.01 to 5% by weight, based on the weight of diol, of a catalytic compound selected from a pyridine, quinoline, picoline, imidazole, benzimidazole, pyrazole, triazole, or a benzotriazole.
US07/434,443 1988-11-16 1989-11-13 Process for the production of cyclic carbonic acid esters Expired - Fee Related US5023346A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3838752 1988-11-16
DE3838752A DE3838752A1 (en) 1988-11-16 1988-11-16 METHOD FOR PRODUCING CYCLIC CARBONIC ESTERS

Publications (1)

Publication Number Publication Date
US5023346A true US5023346A (en) 1991-06-11

Family

ID=6367252

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/434,443 Expired - Fee Related US5023346A (en) 1988-11-16 1989-11-13 Process for the production of cyclic carbonic acid esters

Country Status (5)

Country Link
US (1) US5023346A (en)
EP (1) EP0369249B1 (en)
JP (1) JPH02196783A (en)
DE (2) DE3838752A1 (en)
ES (1) ES2061884T3 (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0617029A1 (en) 1993-03-25 1994-09-28 United States Surgical Corporation Purification of 1,4-dioxan-2-one by crystallization
US6369157B1 (en) 2000-01-21 2002-04-09 Cyclics Corporation Blend material including macrocyclic polyester oligomers and processes for polymerizing the same
US6420048B1 (en) 2001-06-05 2002-07-16 Cyclics Corporation High molecular weight copolyesters from macrocyclic oligoesters and cyclic esters
US6420047B2 (en) 2000-01-21 2002-07-16 Cyclics Corporation Macrocyclic polyester oligomers and processes for polymerizing the same
US6436548B1 (en) 2000-09-12 2002-08-20 Cyclics Corporation Species modification in macrocyclic polyester oligomers, and compositions prepared thereby
US6436549B1 (en) 2001-07-16 2002-08-20 Cyclics Corporation Block copolymers from macrocyclic oligoesters and dihydroxyl-functionalized polymers
US6506909B1 (en) * 2001-12-20 2003-01-14 Ppg Industries Ohio, Inc. Method of making trimethylene carbonate
US6525164B2 (en) 2000-09-01 2003-02-25 Cyclics Corporation Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US6580001B1 (en) * 2001-12-20 2003-06-17 Ppg Industries Ohio, Inc. Method of making trimethylene carbonate
US20030195328A1 (en) * 2002-03-20 2003-10-16 Yi-Feng Wang Catalytic systems
US6787632B2 (en) 2001-10-09 2004-09-07 Cyclics Corporation Organo-titanate catalysts for preparing pure macrocyclic oligoesters
US20040192879A1 (en) * 2002-12-20 2004-09-30 Phelps Peter D. Purification of macrocyclic oligoesters
US20040220334A1 (en) * 2000-01-21 2004-11-04 Yi-Feng Wang Blends containing macrocyclic polyester oligomer and high molecular weight polymer
US20040225058A1 (en) * 2000-01-21 2004-11-11 Tohru Takekoshi Intimate physical mixtures containing macrocyclic polyester oligomer and filler
US6831138B2 (en) 2002-01-07 2004-12-14 Cyclics Corporation Polymer-containing organo-metal catalysts
US20040254281A1 (en) * 2001-06-27 2004-12-16 Thompson Timothy A Isolation, formulation and shaping of macrocyclic oligoesters
US20050137333A1 (en) * 2003-12-19 2005-06-23 Cyclics Corporation Processes for dispersing an impact modifier in a macrocyclic polyester oligomer
US20050282952A1 (en) * 2000-01-21 2005-12-22 Cyclics Corporation Graphite-polyester composites made from macrocyclic polyester oligomers
US20060194946A1 (en) * 2001-06-27 2006-08-31 Cyclics Corporation Processes for shaping macrocyclic oligoesters
US20060235185A1 (en) * 2000-09-01 2006-10-19 Cyclics Corporation Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom
US7256241B2 (en) 2000-01-21 2007-08-14 Cyclics Corporation Methods for polymerizing macrocyclic polyester oligomers using catalyst promoters
US7750109B2 (en) 2000-09-01 2010-07-06 Cyclics Corporation Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer
CN110305324A (en) * 2014-05-07 2019-10-08 旭化成株式会社 Water system composition polycarbonate/polyoxyethylene block copolymer and water system composition comprising it

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3221025A (en) * 1961-12-21 1965-11-30 Gen Electric Aromatic carbonates
US3532715A (en) * 1969-02-24 1970-10-06 Union Carbide Corp Six-membered cyclic carbonates having two olefinically unsaturated substitutents
EP0057360A2 (en) * 1981-01-30 1982-08-11 Bayer Ag Cyclic carbonic acid derivatives, process for their preparation and their use as copolymerisation constituents for the preparation of polycarbonates
US4585566A (en) * 1984-11-21 1986-04-29 Chevron Research Company Carbonate treated dispersants
DE3502106A1 (en) * 1985-01-23 1986-07-24 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING CYCLIC, ALIPHATIC ORTHOCOLIC ACID ESTERS AND NEW CYCLIC ORTHOCOLIC ACID ESTERS
JPS62238279A (en) * 1986-04-08 1987-10-19 Neos Co Ltd 1,3-dioxan-2-one derivative and production thereof
US4727134A (en) * 1985-02-22 1988-02-23 General Electric Company Method for preparing cyclic polycarbonate oligomer mixtures
US4767840A (en) * 1987-03-24 1988-08-30 General Electric Company Cyclic monocarbonate bishaloformates, method for their preparation, and uses thereof
US4870127A (en) * 1986-09-22 1989-09-26 The Dow Chemical Company Poly (alkylene carbonate) polyahls having on the average up to one acid-terminal moiety and salts thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3103136A1 (en) * 1981-01-30 1982-08-26 Bayer Ag, 5090 Leverkusen Novel bicyclic ether carbonates, process for their preparation, and their use

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3221025A (en) * 1961-12-21 1965-11-30 Gen Electric Aromatic carbonates
US3532715A (en) * 1969-02-24 1970-10-06 Union Carbide Corp Six-membered cyclic carbonates having two olefinically unsaturated substitutents
EP0057360A2 (en) * 1981-01-30 1982-08-11 Bayer Ag Cyclic carbonic acid derivatives, process for their preparation and their use as copolymerisation constituents for the preparation of polycarbonates
US4501905A (en) * 1981-01-30 1985-02-26 Bayer Aktiengesellschaft Cyclic carbonic acid derivatives
US4585566A (en) * 1984-11-21 1986-04-29 Chevron Research Company Carbonate treated dispersants
DE3502106A1 (en) * 1985-01-23 1986-07-24 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING CYCLIC, ALIPHATIC ORTHOCOLIC ACID ESTERS AND NEW CYCLIC ORTHOCOLIC ACID ESTERS
US4727134A (en) * 1985-02-22 1988-02-23 General Electric Company Method for preparing cyclic polycarbonate oligomer mixtures
JPS62238279A (en) * 1986-04-08 1987-10-19 Neos Co Ltd 1,3-dioxan-2-one derivative and production thereof
US4870127A (en) * 1986-09-22 1989-09-26 The Dow Chemical Company Poly (alkylene carbonate) polyahls having on the average up to one acid-terminal moiety and salts thereof
US4767840A (en) * 1987-03-24 1988-08-30 General Electric Company Cyclic monocarbonate bishaloformates, method for their preparation, and uses thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ludwig and Piech, JACS 73 (1951), 5779. *
Sarel et al., J. Org. Chem. 24 (1959), 1873. *

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0617029A1 (en) 1993-03-25 1994-09-28 United States Surgical Corporation Purification of 1,4-dioxan-2-one by crystallization
US6420047B2 (en) 2000-01-21 2002-07-16 Cyclics Corporation Macrocyclic polyester oligomers and processes for polymerizing the same
US6994914B2 (en) 2000-01-21 2006-02-07 Cyclics Corporation Macrocyclic polyester oligomers and processes for polymerizing the same
US20040220334A1 (en) * 2000-01-21 2004-11-04 Yi-Feng Wang Blends containing macrocyclic polyester oligomer and high molecular weight polymer
US7230044B2 (en) 2000-01-21 2007-06-12 Cyclics Corporation Intimate physical mixtures containing macrocyclic polyester oligomer and filler
US7151143B2 (en) 2000-01-21 2006-12-19 Cyclics Corporation Blends containing macrocyclic polyester oligomer and high molecular weight polymer
US6369157B1 (en) 2000-01-21 2002-04-09 Cyclics Corporation Blend material including macrocyclic polyester oligomers and processes for polymerizing the same
US20060122307A1 (en) * 2000-01-21 2006-06-08 Cyclics Corporation Intimate physical mixtures containing macrocyclic polyester oligomer and filler
US7256241B2 (en) 2000-01-21 2007-08-14 Cyclics Corporation Methods for polymerizing macrocyclic polyester oligomers using catalyst promoters
US20050282952A1 (en) * 2000-01-21 2005-12-22 Cyclics Corporation Graphite-polyester composites made from macrocyclic polyester oligomers
US6639009B2 (en) 2000-01-21 2003-10-28 Cyclis Corporation Macrocyclic polyester oligomers and processes for polymerizing the same
US20050245676A1 (en) * 2000-01-21 2005-11-03 Cyclics Corporation Macrocyclic polyester oligomers and processes for polymerizing the same
US20040011992A1 (en) * 2000-01-21 2004-01-22 Cyclics Corporation Macrocyclic polyester oligomers and processes for polymerizing the same
US6960626B2 (en) 2000-01-21 2005-11-01 Cyclics Corporation Intimate physical mixtures containing macrocyclic polyester oligomer and filler
US20040225058A1 (en) * 2000-01-21 2004-11-11 Tohru Takekoshi Intimate physical mixtures containing macrocyclic polyester oligomer and filler
US20060235185A1 (en) * 2000-09-01 2006-10-19 Cyclics Corporation Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom
US6525164B2 (en) 2000-09-01 2003-02-25 Cyclics Corporation Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US8283437B2 (en) 2000-09-01 2012-10-09 Cyclics Corporation Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom
US7767781B2 (en) 2000-09-01 2010-08-03 Cyclics Corporation Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom
US7750109B2 (en) 2000-09-01 2010-07-06 Cyclics Corporation Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer
US6855798B2 (en) 2000-09-01 2005-02-15 Cyclics Corporation Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US7309756B2 (en) 2000-09-01 2007-12-18 Cyclics Corporation Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US20060128936A1 (en) * 2000-09-01 2006-06-15 Cyclics Corporation Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US7022806B2 (en) 2000-09-01 2006-04-04 Cyclics Corporation Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US20050176917A1 (en) * 2000-09-01 2005-08-11 Cyclics Corporation Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US20030236386A1 (en) * 2000-09-01 2003-12-25 Faler Gary R. Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters
US6713601B2 (en) 2000-09-12 2004-03-30 Cyclics Corporation Species modification in macrocyclic polyester oligomers, and compositions prepared thereby
US6436548B1 (en) 2000-09-12 2002-08-20 Cyclics Corporation Species modification in macrocyclic polyester oligomers, and compositions prepared thereby
US6420048B1 (en) 2001-06-05 2002-07-16 Cyclics Corporation High molecular weight copolyesters from macrocyclic oligoesters and cyclic esters
US20040254281A1 (en) * 2001-06-27 2004-12-16 Thompson Timothy A Isolation, formulation and shaping of macrocyclic oligoesters
US7666517B2 (en) 2001-06-27 2010-02-23 Cyclics Corporation Isolation, formulation, and shaping of macrocyclic oligoesters
US7304123B2 (en) 2001-06-27 2007-12-04 Cyclics Corporation Processes for shaping macrocyclic oligoesters
US20070037464A1 (en) * 2001-06-27 2007-02-15 Cyclics Corporation Isolation, formulation, and shaping of macrocyclic oligoesters
US7071291B2 (en) 2001-06-27 2006-07-04 Cyclics Corporation Isolation, formulation and shaping of macrocyclic oligoesters
US20060194946A1 (en) * 2001-06-27 2006-08-31 Cyclics Corporation Processes for shaping macrocyclic oligoesters
US6436549B1 (en) 2001-07-16 2002-08-20 Cyclics Corporation Block copolymers from macrocyclic oligoesters and dihydroxyl-functionalized polymers
US7615511B2 (en) 2001-10-09 2009-11-10 Cyclics Corporation Organo-titanate catalysts for preparing pure macrocyclic oligoesters
US6787632B2 (en) 2001-10-09 2004-09-07 Cyclics Corporation Organo-titanate catalysts for preparing pure macrocyclic oligoesters
US20050054862A1 (en) * 2001-10-09 2005-03-10 Cyclics Corporation Organo-titanate catalysts for preparing pure macrocyclic oligoesters
US6580001B1 (en) * 2001-12-20 2003-06-17 Ppg Industries Ohio, Inc. Method of making trimethylene carbonate
US6506909B1 (en) * 2001-12-20 2003-01-14 Ppg Industries Ohio, Inc. Method of making trimethylene carbonate
US6831138B2 (en) 2002-01-07 2004-12-14 Cyclics Corporation Polymer-containing organo-metal catalysts
US20050227861A1 (en) * 2002-03-20 2005-10-13 Cyclics Corporation Catalytic systems
US20030195328A1 (en) * 2002-03-20 2003-10-16 Yi-Feng Wang Catalytic systems
US7186666B2 (en) 2002-03-20 2007-03-06 Cyclics Corporation Catalytic systems
US6906147B2 (en) 2002-03-20 2005-06-14 Cyclics Corporation Catalytic systems
US6962968B2 (en) 2002-12-20 2005-11-08 Cyclics Corporation Purification of macrocyclic oligoesters
US20040192879A1 (en) * 2002-12-20 2004-09-30 Phelps Peter D. Purification of macrocyclic oligoesters
US20050137333A1 (en) * 2003-12-19 2005-06-23 Cyclics Corporation Processes for dispersing an impact modifier in a macrocyclic polyester oligomer
CN110305324A (en) * 2014-05-07 2019-10-08 旭化成株式会社 Water system composition polycarbonate/polyoxyethylene block copolymer and water system composition comprising it
CN110305324B (en) * 2014-05-07 2022-01-28 旭化成株式会社 Polycarbonate/polyoxyethylene block copolymer for aqueous composition, and aqueous composition containing same

Also Published As

Publication number Publication date
DE3838752A1 (en) 1990-05-17
ES2061884T3 (en) 1994-12-16
DE58906574D1 (en) 1994-02-10
EP0369249B1 (en) 1993-12-29
EP0369249A3 (en) 1990-12-19
EP0369249A2 (en) 1990-05-23
JPH02196783A (en) 1990-08-03

Similar Documents

Publication Publication Date Title
US5023346A (en) Process for the production of cyclic carbonic acid esters
US3661923A (en) Polyfunctional polyol ester oxazolidines
US2924607A (en) Preparation of oxetanes
US2983744A (en) Heterocycles
US6423862B1 (en) Synthesis of vinyl carbonates for use in producing vinyl carbamates
US20160145232A1 (en) 2-oxo-1,3-dioxolane-4-acyl halides, their preparation and use
US4939170A (en) Substituted aminophenyl carbamates
US20220380311A1 (en) Method for producing aromatic heterocyclic ring-substituted difluoroacetic acid derivative
US5260474A (en) Pesticidal substituted aminophenyl carbamates
JP6944141B2 (en) Isocyanuric acid derivative having an alkoxyalkyl group and its production method
JP4378664B2 (en) Method for producing isocyanate group-containing siloxane compound
JPS594422B2 (en) Process for producing N-chloroformyl carbonate amide
EP0508430A1 (en) Process for the preparation of bisoxazolidines containing urethane groups
EP0786459B1 (en) Process for the preparation of a hetero-bicyclic alcohol enantiomer
US4851550A (en) Process for the preparation of cyclic aliphatic orthocarbonic esters new cyclic orthocarbonic esters
US4332744A (en) Unsymmetrical polynitrocarbonates and methods of preparation
CA1087618A (en) Process for preparing perfluoro-4-oxo-2,5-dimethyl-2- fluorocarbonyl-1,3-dioxolane
JPS584779A (en) Manufacture of 2-alkoxy-(1,3)-dioxolane
US3758510A (en) Process for producing fluorinated cyclic ketals
US10160694B2 (en) Agent for introducing protecting group for hydroxy group and/or mercapto group
US4447635A (en) N-Substituted imido-dicarboxylic acid diaryl ester compounds and herbicide intermediates
US3632820A (en) Process for the production of fluorinated benzodioxanes
US4935534A (en) 1-(N-formylamino)-2,4-dicyanobutane and a process for its production
KR102687147B1 (en) Alkylation of picolinamide with substituted chloroacyls using a crown ether catalyst
US3090802A (en) Alkylene glycol borates

Legal Events

Date Code Title Description
AS Assignment

Owner name: BAYER AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:SCHON, NORBERT;BUYSCH, HANS-JOSEF;REEL/FRAME:005171/0604

Effective date: 19891018

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 19990611

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362